二苯基亚砜、苯甲酸与轻稀土高氯酸四元配合物的合成表征及光致发光

合成并表征了高氯酸稀土与二苯基亚砜、苯甲酸的四种四元配合物。经元素分析、稀土络合滴定、摩尔电导率及差热-热重分析,表明四元配合物组成为[REL5L′(ClO4)] (ClO4) (RE= La,Pr,Nd,Eu;L=C6H5SOC6H5,L′=C6H5COO-)。在红外光谱中,第一配体二苯基亚砜的νS O的特征吸收峰出现在1 037cm-1处,而各稀土配合物的νS O向低波数移动到984 ～989 cm-1,红移50 cm-1左右,表明稀土离子与亚砜基团的氧原子之间发生配位作用。第二配体苯甲酸钠的反对称伸缩振动吸收峰νas(COO -)出现在1 550 cm-1,对称伸缩振动吸收峰νs(COO -)出现在1 416 cm-1处,羧基伸缩振动吸收频率差Δn[νas(COO -)-νs(COO -)]值为134cm-1;在所有配合物的红外光谱图中νas(COO -)向高波数方向发生了位移,而νs(COO -)向低波数方向发生了位移,并且Δn值均大于钠盐的Δn值,由此可以认为配合物中羧基是通过单齿方式与稀土离子配位。测定了配合物在丙酮溶液中的摩尔电导率,根据配合物在常见有机溶剂中的摩尔电导率与正负离子的关系结合配合物的红外光谱中高氯酸根离子的四条特征吸收带,表明配合物为1:1型电解质,两个ClO4-无机抗衡阴离子,其中一个在外界,一个进入内界与稀土离子配位。配合物的荧光发射光谱表明,四元配合物的荧光强度比二苯基亚砜高氯酸稀土二元配合物的荧光强度提高469%。磷光光谱表明苯甲酸三重态能级的下限和二苯亚砜三重态能级的上限重叠,导致三重态能级范围扩大,由此可见第二配体的加入提高了配体的三重态能级与Eu3 离子5D0能级的匹配程度。同时在配合物的荧光发射光谱中还可以看到铕离子的电偶极跃迁强度大于磁偶极跃迁,表明稀土离子不处于晶体场的对称中心。在四元配合物中,由于第二配体的加入,往往会降低配合物的对称性,从而增强稀土离子的荧光强度。本文合成的稀土配合物具有良好的荧光性能,而且在室温下稳定,溶解性好,分解温度较高。     

柔性有机电致发光器件导电基板的工艺性能

在聚对苯二甲酸乙二醇酯(PET)柔性衬底上采用直流磁控溅射技术制备了氧化铟锡(ITO)透明导电薄膜,研究了衬底温度、溅射功率和溅射压强等工艺条件对薄膜光电性能的影响,并利用原子力显微镜(AFM)表征了衬底及ITO薄膜的表面形貌。结果表明,在PET衬底温度50℃、溅射功率100W和溅射压强2.66×10-1Pa的条件下,可以得到低方阻(50Ω/□)和高透过率(>90%)的透明导电薄膜。以此柔性ITO衬底为阳极,制备了结构为PET/ITO/NPB/Alq3/Mg∶Ag的柔性有机电致发光器件,在驱动电压为13V时,器件的发光亮度达到了2834cd/m2。     

InGaN蓝光与CdTe纳米晶基白光LED

报道了倒装焊InGaN蓝光LED与黄光CdTe纳米晶的复合结构。利用蓝光作为CdTe纳米晶的激发源,通过光的下转换机制,将部分蓝光转化为黄光,复合发射出白光。室温下正向驱动电流为10mA时,发光色品坐标为x=0.29,y=0.30。实验表明,该复合结构白光LED的一大优点在于,复合光的色品坐标几乎不随正向驱动电流大小变化,颜色稳定。     

Light-Responsive Hexagonal Assemblies of Triangular Azo Dyes

The rational design of small building block molecules and understanding their molecular assemblies are of fundamental importance in creating new stimuli-responsive organic architectures with desired shapes and functions. Based on the experimental results of light-induced conformational changes of four types of triangular azo dyes with different terminal functional groups, as well as absorption and fluorescence characteristics associated with their molecular assemblies, we report that aggregation-active emission enhancement (AIEE)-active compound (1) substituted with sterically crowded tert-butyl (t-Bu) groups showed approximately 35% light-induced molecular switching and had a strong tendency to assemble into highly stable hexagonal structures with AIEE characteristics. Their sizes were regulated from nanometer-scale hexagonal rods to micrometer-scale sticks depending on the concentration. This is in contrast to other triangular compounds with bromo (Br) and triphenylamine (TPA) substituents, which exhibited no photoisomerization and tended to form flexible fibrous structures. Moreover, non-contact exposure of the fluorescent hexagonal nanorods to ultraviolet (UV) light led to a dramatic hexagonal-to-amorphous structure transition. The resulting remarkable variations, such as in the contrast of microscopic images and fluorescence characteristics, were confirmed by various microscopic and spectroscopic measurements.     

In Vitro and In Vivo Human Body Odor Analysis Method Using GO:PANI/ZNRs/ZIF−8 Adsorbent Followed by GC/MS

Among various volatile organic compounds (VOCs) emitted from human skin, trans-2-nonenal, benzothiazole, hexyl salicylate, α-hexyl cinnamaldehyde, and isopropyl palmitate are key indicators associated with the degrees of aging. In our study, extraction and determination methods of human body odor are newly developed using headspace-in needle microextraction (HS-INME). The adsorbent was synthesized with graphene oxide:polyaniline/zinc nanorods/zeolitic imidazolate framework-8 (GO:PANI/ZNRs/ZIF−8). Then, a wire coated with the adsorbent was placed into the adsorption kit to be directly exposed to human skin as in vivo sampling and inserted into the needle so that it was able to be desorbed at the GC injector. The adsorption kit was made in-house with a 3D printer. For the in vitro method, the wire coated with the adsorbent was inserted into the needle and exposed to the headspace of the vial. When a cotton T-shirt containing body odor was transferred to a vial, the headspace of the vial was saturated with body odor VOCs. After volatile organic compounds were adsorbed in the dynamic mode, the needle was transferred to the injector for analysis of the volatile organic compounds by gas chromatography/mass spectrometry (GC/MS). The conditions of adsorbent fabrication and extraction for body odor compounds were optimized by response surface methodology (RSM). In conclusion, it was able to synthesize GO:PANI/ZNRs/ZIF−8 at the optimal condition and applicable to both in vivo and in vitro methods for body odor VOCs analysis.     

Metabolic Profile of Agropyron repens (L.) P. Beauv. Rhizome Herbal Tea by HPLC-PDA-ESI-MS/MS Analysis

Agropyron repens (L.) P. Beauv. (couch grass) is a world-wide infesting rhizomatous plant with pharmacological applications. Chemical research is focused on its allelopathic and anti-inflammatory components, which are mainly present in the essential oil. Conversely, the aqueous extracts have been sparingly investigated, although the herbal tea is by far the most used formulation. To fill the gap, the metabolic profile of Agropyron repens rhizome herbal tea was investigated by electrospray ionization (ESI) tandem–mass spectrometry (MS/MS); the phenolic profile was investigated by HPLC-PDA-ESI-MS/MS. ESI-MS fingerprinting was provided, evidencing diagnostic ions for saccharides, organic acids and amino acids. The HPLC-PDA-ESI-MS/MS analysis evidenced at least 20 characteristic phenolic compounds, the most representative being caffeoyl and feruloyl quinic esters, followed by coumaric, caffeic and ferulic acids, and hesperidin among flavonoids. In addition, the essential amino acid tryptophan was identified for the first time. The results suggest new perspectives of applications for Agropyron repens rhizome.     

基于高次余弦散射分布的空间卫星可见光特性

基于几何光学和辐射理论,研究了空间卫星的可见光散射特性.空间卫星的背景辐射主要包括太阳的直接辐射和地球及大气的散射辐射,根据目标的结构特性与背景特性建立了空间卫星的几何模型和光照模型.分析目标表面状况,入射到目标表面的光线近似服从高次余弦散射分布,根据能量守恒定理及表面材料的高次余弦散射分布特性建立了目标散射特性的数学模型.通过矢量坐标变换确定太阳、地球、观测卫星在目标本体坐标系下的相对位置关系.根据给定的几何尺寸和表面物性参量仿真获得了目标在探测器入瞳处的能量分布及星等特征,目标本体与太阳帆板在探测器入瞳处的辐照度最大量级均为10-12 W/m2.仿真结果表明太阳帆板在目标特性分析时不可忽略,为空间目标的可见光探测提供参考数据.     

结构光测量中的高精度相位误差补偿算法

在模拟分析投影仪伽马非线性对相位误差影响的基础上,提出一种直接分析投影光栅特征并建立相位误差查找表的算法.对相位误差进行补偿.该算法通过分析一组投射到标准白色平板上的光栅图像,确定光栅相位值与相位误差的对应关系,并量化存储在一个查找表中,测量过程中使用查找表对相位误差进行补偿.实验结果表明.该方法可大大降低由投影仪伽马非线性引起的相位误差,系统测量精度达到0.043 mm,比误差补偿前提高了5.6倍.     

离焦激光直写的线宽稳定方法

为了提高激光直写加工衍射光学元件时的线条质量,提出一种离焦激光直写的线宽稳定方法.该方法通过同时调节激光功率和离焦量,使光刻胶的曝光阈值处于线宽对曝光量的变化率较小位置,从而可以弱化线宽对实际曝光量或光刻胶阈值等变化的敏感度,提高利用离焦方法进行衍射光学元件制作时的线宽稳定性.推导了稳定线宽后的光功率控制模型和线宽模型,模型中的变量仅为离焦量,降低了光功率控制的复杂性.利用632.8 nm的He-Ne激光和NA-0.1的物镜在CCD上对采用该方法后的离焦线宽模型进行验证,实验结果与理论模型吻合较好.该方法对于线宽稳定度较高的衍射光学元件制作具有重要价值.     

2,2-双(4-氯-2-氟苄基)丙二酸二乙酯的晶体结构和密度泛函理论研究

标题化合物是一个重要的精细化工中间体,可用于制备嘧啶类、吡唑类等产品.本文利用红外光谱(IR)、质谱(MS)、核磁共振氢谱(1 H NMR)、核磁共振碳谱(13 C NMR)和X-射线单晶衍射对此化合物进行了表征,并在B3LYP/6-311G(d,p)模式下使用密度泛函理论(DFT)计算了此化合物的最稳定晶体结构以及最...